JPH02227195A - Scale prevention method - Google Patents
Scale prevention methodInfo
- Publication number
- JPH02227195A JPH02227195A JP1328627A JP32862789A JPH02227195A JP H02227195 A JPH02227195 A JP H02227195A JP 1328627 A JP1328627 A JP 1328627A JP 32862789 A JP32862789 A JP 32862789A JP H02227195 A JPH02227195 A JP H02227195A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- water
- soluble salt
- formula
- water soluble
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 6
- 230000002265 prevention Effects 0.000 title 1
- 150000003839 salts Chemical class 0.000 claims abstract description 19
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 17
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- ZJAOAACCNHFJAH-UHFFFAOYSA-N phosphonoformic acid Chemical compound OC(=O)P(O)(O)=O ZJAOAACCNHFJAH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 5
- 229960005102 foscarnet Drugs 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract 2
- 239000002253 acid Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 9
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 23
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 abstract 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 230000002401 inhibitory effect Effects 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 150000003851 azoles Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- PTMHPRAIXMAOOB-UHFFFAOYSA-L phosphoramidate Chemical compound NP([O-])([O-])=O PTMHPRAIXMAOOB-UHFFFAOYSA-L 0.000 description 4
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000008233 hard water Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- -1 amine salts Chemical class 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002455 scale inhibitor Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- SCRFJYDVSBOEMJ-UHFFFAOYSA-N 2-ethyl-3-phosphonobutanedioic acid Chemical group CCC(C(O)=O)C(C(O)=O)P(O)(O)=O SCRFJYDVSBOEMJ-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- SZHQPBJEOCHCKM-UHFFFAOYSA-N 2-phosphonobutane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(P(O)(O)=O)(C(O)=O)CC(O)=O SZHQPBJEOCHCKM-UHFFFAOYSA-N 0.000 description 1
- NNRAOBUKHNZQFX-UHFFFAOYSA-N 2H-benzotriazole-4-thiol Chemical compound SC1=CC=CC2=C1NN=N2 NNRAOBUKHNZQFX-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 150000001204 N-oxides Chemical class 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- OMAAXMJMHFXYFY-UHFFFAOYSA-L calcium trioxidophosphanium Chemical class [Ca+2].[O-]P([O-])=O OMAAXMJMHFXYFY-UHFFFAOYSA-L 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- AAYRWMCIKCRHIN-UHFFFAOYSA-N propane-1-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CCCS(O)(=O)=O AAYRWMCIKCRHIN-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Sorption Type Refrigeration Machines (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Holo Graphy (AREA)
- Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は水系の処理に関し、及びより詳細には冷却系に
おいて生成するスケールを抑制し、除去することに関す
る。DETAILED DESCRIPTION OF THE INVENTION This invention relates to the treatment of water systems, and more particularly to inhibiting and removing scale that forms in cooling systems.
本発明を要約すれば、水系に
（ｉ）カルボン酸及びホスフォン酸基である少なくとも
３個の酸基を含み、少なくとも一つの酸基はカルボン酸
基であり、及び少なくとも一つの酸基はホスフォン酸基
であり、少なくとも該３個の酸基は炭素原子に結合して
いる、ホスフ才ノカルボン酸、又はその水溶性の塩、
（Ｌｉ、）式：
％式％
上式中
Ｒ３及びＲ８は独立に水素、アルキル、特にｌないし４
炭素厚子のアルキル、
−（ＣＨ＊）、ＰＯｓＨｘ又は−（ＣＨ，）、Ｃ０ＯＨ
を表し、及びｎはｌ又は２である、
を有するアミノホスフォン酸又はその水溶性の塩、及び
（ｉｉ）式
％式％（）
上式中
Ｒｒ、Ｒｚ及びｎは上記の通りである、のアミノホスフ
ォン酸酸化物、又はその水溶性の塩、
を添加することから成る、水系、典型的には冷却系中の
硬水を処理する方法が記載されていることである。To summarize the invention, the aqueous system comprises (i) at least three acid groups that are carboxylic acid and phosphonic acid groups, at least one acid group is a carboxylic acid group, and at least one acid group is a phosphonic acid group; a phosphatinocarboxylic acid, or a water-soluble salt thereof, in which at least the three acid groups are bonded to carbon atoms, (Li,) formula: % formula % where R3 and R8 are independently hydrogen, alkyl, especially l to 4
Carbon thick alkyl, -(CH*), POsHx or -(CH,), C0OH
, and n is l or 2, and (ii) an aminophosphonic acid or a water-soluble salt thereof having the formula % formula % () in which Rr, Rz and n are as above, A method is described for treating hard water in an aqueous system, typically a cooling system, comprising adding an aminophosphonic acid oxide, or a water-soluble salt thereof.
水、特に硬水が加熱されると、水と接触する表面にスケ
ールが生じることは周知である。こうしてスケールは冷
却水と接触する熱い表面上に生成する。スケールは又ボ
イラー中にも生じる。It is well known that when water, especially hard water, is heated, scale forms on surfaces that come into contact with the water. Scale thus forms on hot surfaces that come into contact with cooling water. Scale also forms in boilers.
各種の異なる合成及び天然産の薬品がスケールの生成を
試み及び減少させるために、水への添加剤として使用さ
れてきた。この理由はスケールが生じた時には熱交換表
面を横切る熱伝達の減少が起伴り、或場合には局部的な
過熱が起こることもあるからである。A variety of different synthetic and naturally occurring chemicals have been used as additives to water to attempt and reduce scale formation. This is because scaling is associated with a reduction in heat transfer across the heat exchange surface, and in some cases localized overheating may occur.
指摘されたように、水溶性の重合体、ホスフォネート及
びキレート化剤がスケール生成を防止するために使用さ
れてきた。本発明により、三種の特殊な形式のホスフォ
ネートの組み合わせを使用することによって特に良好な
スケールの抑制が得られることが新規に見出された。本
発明によれば、水系に
（ｉ）カルボン酸及びホスフオン酸基である少なくとも
３個の酸基を含み、少なくとも一つの酸基はカルボン酸
基であり、及び少なくとも一つの酸基はホスフオン酸基
であり、少なくとも該３例の酸基は炭素原子に結合して
いる、ホス７オノカルボン酸、又はその水溶性の塩、
（ｉ）式：
％式％
上式中
Ｒ，及びＲ２は独立に水素、アルキル、特に１ないし４
炭素原子のアルキル、
（ＣＨ＊）、Ｐ ０３Ｈ２又は−（ＣＨ，）、Ｃ０ＯＨ
を表し、及びｎはｌ又は２である、
を有するアミノホスフォン酸又はその水溶性の塩、及び
（ｉｉｉ）式
％式％）
上式中
Ｒｒ、Ｒｉ及びｎは上記の通りである、のアミノホスフ
ォン酸酸化物、又はその水溶性の塩、
を添加することから成る、水性系、特にボイラー水又は
冷却系を処理する方法が提供される。As noted, water-soluble polymers, phosphonates and chelating agents have been used to prevent scale formation. In accordance with the present invention, it has now been newly discovered that particularly good scale control can be obtained by using a combination of three special types of phosphonates. According to the invention, the aqueous system comprises (i) at least three acid groups that are carboxylic acid and phosphonic acid groups, at least one acid group is a carboxylic acid group, and at least one acid group is a phosphonic acid group; and at least the three acid groups are bonded to carbon atoms, phos-7-onocarboxylic acid or a water-soluble salt thereof, (i) Formula: %Formula% In the above formula, R and R2 are independently hydrogen , alkyl, especially 1 to 4
Alkyl of a carbon atom, (CH*), P 03H2 or -(CH,), C0OH
, and n is l or 2, and (iii) an aminophosphonic acid or a water-soluble salt thereof having the formula %) in which Rr, Ri and n are as above. A method is provided for treating an aqueous system, in particular a boiler water or cooling system, comprising adding an aminophosphonic acid oxide, or a water-soluble salt thereof.
驚くべきことには、これらの三種のホスフォネートを組
み合わせて使用すれば、任意のホスフォネートを個々に
使用するか又はそれらの二種を任意に組み合わせて使用
するよりも一層効果的なスケールの抑制を与えることが
見出された。更に、特定のホスフォノカルボン酸及びア
ミノホスフォネートの使用が提案されているが、これは
冷却系における腐食を抑制する目的のためであって、ス
ケールの防止の目的のためではなかった。Surprisingly, the combination of these three phosphonates provides more effective scale control than any of the phosphonates individually or any combination of the two. It was discovered that Furthermore, the use of certain phosphonocarboxylic acids and aminophosphonates has been proposed, but this has been for the purpose of inhibiting corrosion in cooling systems, and not for the purpose of preventing scale.
本発明はスケールが主として炭酸カルシウムの生成によ
り、典型的には、冷却水温度、例えば４０−５０℃にお
いて、３００ｐｐｍ Ｍ アルカリ度を有すると共に、
少なくとも３００ｐｐ個のカルシウム硬度を有し、又は
異なる水質条件下で等価な量を有する硬水系において特
に適用性を有している。アミノホスフォネートの対応す
るＮ−酸化物への変換は、最初のアミノホスフォネート
よりもカルシウム許容度（ｔｏｌｅｒａｎｃｅ）の低い
物質をもたらすから、組み合わせが非常に効果的である
ことは特に驚くべきである。カルシウム許容度が低いこ
とにより、カルシウムホス７オネートの沈澱を生じて、
スケール抑制剤としてのホスフォネートを消費するだけ
でなく、カルシウムホスフォネートのスケール化を引き
起こすので、当業者はカルシウム許容度が低いことは、
高いカルシウム含量を有する水中でスケール抑制剤とし
て使用される添加剤には有害であることと理解されよう
。The present invention provides that the scale typically has an alkalinity of 300 ppm M at cooling water temperature, e.g. 40-50°C, primarily due to the formation of calcium carbonate,
It has particular applicability in hard water systems with a calcium hardness of at least 300 pp or an equivalent amount under different water quality conditions. It is particularly surprising that the combination is so effective since conversion of the aminophosphonate to the corresponding N-oxide results in a substance with lower calcium tolerance than the initial aminophosphonate. It is. Poor calcium tolerance results in precipitation of calcium phos7onate,
A person skilled in the art understands that low calcium tolerance does not only consume phosphonates as scale inhibitors, but also causes scaling of calcium phosphonates.
It will be appreciated that additives used as scale inhibitors in waters with high calcium content are harmful.
使用されるアミノホスフォネートは、好適にはＲ１及び
Ｒ２の両者がメチルホスフォネートを表す化合物であり
、即ち該化合物はアミノトリス（メチレンホスホンｍ）
（ＡＴＭＰ）である。使用される酸化物は必ずしも使用
されるアミノホスフォネートに対応する酸化物である必
要はないが、通常はそうであることが便利である。好適
な酸化物はアミノトリス（メチレンホスホンＩＩ）−Ｎ
−オキシド（即ち、Ｒ，とＲ２が共にメチルホスフォン
酸を表す（ＡＴＶＰ−Ｎ−０））である。The aminophosphonate used is preferably a compound in which both R1 and R2 represent methylphosphonate, ie the compound is aminotris(methylenephosphon m)
(ATM). The oxide used does not necessarily have to be the oxide corresponding to the aminophosphonate used, although it is usually convenient to do so. A preferred oxide is aminotris(methylenephosphone II)-N
-oxide (ie, R and R2 both represent methylphosphonic acid (ATVP-N-0)).
成分（凰）は好適には一般式
上式中
Ｒは水素、最高４炭素原子を有するアルキル、アルケニ
ル又はアルキニル；フェニル：３ないし６炭素原子を有
するシクロアルキル、ベンジル；フェネチル又は
上式中Ｒ′は水素、ｌないし４炭素原子又はカルホキシ
ルを有するアルキル
は水素又はメチルであり・、及びＲ〜はカルボキシル又
はホス７オネートである、
である、
を有している。商業的に利用し得る材料である、２−ホ
スホノブタン−１．２．４−１−リカルポン酸（ＰＢＴ
Ｃ）が特に好適である。他の好適な材料は２，４−ジ′
ホスホノブタンー１．２ージカルボン酸である。The component (凰) preferably has the general formula R' in the above formula: hydrogen, alkyl, alkenyl or alkynyl having up to 4 carbon atoms; phenyl: cycloalkyl having 3 to 6 carbon atoms, benzyl; phenethyl or R' in the above formula; is hydrogen, the alkyl having 1 to 4 carbon atoms or carboxyl is hydrogen or methyl, and R~ is carboxyl or phos7onate. 2-phosphonobutane-1.2.4-1-licarponic acid (PBT) is a commercially available material.
C) is particularly preferred. Other suitable materials include 2,4-di'
It is phosphonobutane-1,2-dicarboxylic acid.
ホス７オネートが塩の形態で使用されるならば、典型的
な塩はアルカリ金属、特にナトリウム又はカリウム、ア
ンモニウム又は七ノー、ジー又はトリーエタノールアミ
ンのような低級アミン塩を含んでいる。If the phos7onate is used in the form of a salt, typical salts include alkali metal, especially sodium or potassium, ammonium or lower amine salts such as 7-, di-, or tri-ethanolamine.
水系中に添合される各成分の合計量は広範な範囲内で変
わることができるが、一般には０．１ないし５０ｐｐ個
の量の各成分が存在する。好適には各成分の量は１．０
ないし２ ０ ｐ ｐｍｓ 特ｊ： １ないし１２ｐｐ
ｍである。各成分は系に別個に添加することができるが
、通常配合物としてそれらを一緒に添加することが便利
である。The total amount of each component incorporated into the aqueous system can vary within a wide range, but generally there will be an amount of 0.1 to 50 pp of each component. Preferably the amount of each component is 1.0
to 20 pp pms Special J: 1 to 12 pp
It is m. Although each component can be added to the system separately, it is usually convenient to add them together as a formulation.
従って本発明は又一般には水溶液として、上記のような
成分（１％ ロ及びｉ）を含む、水系に添加するのに適
当な組成物を提供する。各成分が沈澱しなければ、任意
の水を使用することができる；塩基イオン交換水の使用
が好適である。The invention therefore also provides compositions suitable for addition to aqueous systems, generally as an aqueous solution, containing components (1% b and i) as described above. Any water can be used as long as the components do not precipitate; the use of base ion-exchanged water is preferred.
こうした組成物中において、成分（ｉ）は通常１５ない
し９０重量％、好適には４０ないし７０重量％、及び特
に５５ないし４５重量％（活性物）の量で存在する。ア
ミノホスホン酸（成分（ｎ））の量は一般に３５ないし
５重量％、好適には３０ないし１５重量％及び特に２０
ないし２５重量％（活性物）あるが、酸化物の量は一般
に５０ないし５重量％、好適には３０ないし１５重量％
、及び特に２５ないし３０重量％（活性物）である。In such compositions, component (i) is usually present in an amount of 15 to 90% by weight, preferably 40 to 70% and especially 55 to 45% by weight (active). The amount of aminophosphonic acid (component (n)) is generally 35 to 5% by weight, preferably 30 to 15% by weight and especially 20% by weight.
The amount of oxide is generally between 50 and 5% by weight, preferably between 30 and 15% by weight (actives).
, and especially 25 to 30% by weight (active).
好適な組成物は塩基交換された又は軟水中において、３
ないし６重量％（活性物）のＰＢＴＣ，１。A preferred composition is in base-exchanged or soft water.
PBTC, 1 to 6% by weight (active).
５ないし３重量％（活性物）のＡＴＶＰ及び１．５ない
し３重量％（活性物）のＡＴＭＰ−Ｎ−０から成る。It consists of 5 to 3% by weight (active) ATVP and 1.5 to 3% (active) ATMP-N-0.
三種のホスホネート以外に、水系の処理に使用される他
の薬品を組成物中に添合すること又は水系に添加するこ
とが可能である。こうした材料は一般に１０００ないし
５０００の分子量を有するポリアクリル酸又はポリメタ
クリル酸のようなスケール抑制重合体、スルホン化重合
体、例えばアクリル又はメタクリル酸と２−メチル−２
−アクリルアミドプロパンスルホン酸の共重合体、及び
マレイン酸とアルキルスルホン酸又はスチレンスルホン
酸の共重合体、及びベンゾトリアゾール、トリルトリア
ゾール、及びメルカプトベンゾトリアゾールのようなア
ゾール類を含んでいる。Besides the three phosphonates, it is possible to incorporate other chemicals used in the treatment of water systems into the composition or add them to the water system. Such materials generally include scale-inhibiting polymers such as polyacrylic acid or polymethacrylic acid, sulfonated polymers, such as acrylic or methacrylic acid and 2-methyl-2
- copolymers of acrylamide propane sulfonic acid, and copolymers of maleic acid and alkyl sulfonic acid or styrene sulfonic acid, and azoles such as benzotriazole, tolyltriazole, and mercaptobenzotriazole.
かようなスケール抑制重合体及び分散剤は通常水系にお
いてｌないしｌＯ１好適には１ないし５ｐｐ個の量で存
在するが、アゾール類は通常ｌないしｌＯ１好適には１
ないし３ｐｐ個の量で存在する。本発明による組成物中
には、スケール抑制重合体及び分散剤は通常３０ないし
５０重量％の量で存在し、アゾール類は通常ホス７オネ
ートの全重量に対して２０ないし５０重量％の量に存在
している。上記に挙げた好適な配合物中においては、ス
ケール抑制重合体及び分散剤は一般には２ないし３重量
％の量で存在するが、対応するアゾール類の量は１ない
し２重量％である。Such scale-inhibiting polymers and dispersants are usually present in the aqueous system in an amount of 1 to 1 O 1 , preferably 1 to 5 ppm, whereas azoles are usually present in an amount of 1 to 1 O 1 , preferably 1 to 5 ppm.
It is present in an amount of 3pp to 3pp. In the compositions according to the invention, scale-inhibiting polymers and dispersants are usually present in an amount of 30 to 50% by weight, and azoles are usually present in an amount of 20 to 50% by weight relative to the total weight of the phospho7onate. Existing. In the preferred formulations mentioned above, the scale-inhibiting polymer and dispersant are generally present in an amount of 2 to 3% by weight, while the corresponding amount of azoles is 1 to 2% by weight.
下記の実施例は本発明を更に例を挙げて説明するもので
ある。The following examples further illustrate the invention.
実施例
熱交換機及び冷却塔の使用を含む実験室的にシミレート
した冷却系について試験が行われ、その条件及び試験の
結果は下記の通りである：系統水： ６００ｐｐｍカ
ルシウム硬度／６００ｐｐｍ″Ｍ＃アルカリ度
水温：
４０℃
熱交換機中の水流速度：
ｐＨ：
０．３フイ一ト毎秒
９．３
ＢＴＣ
３，０
ＢＴＣ
ＡＴＭＰ
ＡＴＭＰ−Ｎ−０
６，０
６，０
６，０
３３８車
２２５本
２３９京
もし何も添加剤を使用しないならば、スケールの生成が
起こり、更に炭酸カルシウムが本体の水相中に沈澱して
極めて重大な水系の汚染を引き起こす。EXAMPLE Tests were conducted on a laboratory simulated cooling system involving the use of a heat exchanger and a cooling tower, and the conditions and test results were as follows: System water: 600 ppm calcium hardness/600 ppm''M# alkaline. Water temperature: 40°C Water flow rate in heat exchanger: pH: 0.3 feet per second 9.3 BTC 3,0 BTC ATMP ATMP-N-0 6,0 6,0 6,0 338 cars 225 cars 239 quintillion If no additives are used, scale formation will occur and further calcium carbonate will precipitate into the body's aqueous phase, causing very serious contamination of the water system.
三種のホスフォネートの組み合わせの使用は、個々の成
分又は三種の成分の二種の組み合わせの挙動から予想さ
れるよりも極めて少ないスケールの生成をもたらすこと
がこうして理解出来よう。It can thus be seen that the use of a combination of three phosphonates results in much less scale production than would be expected from the behavior of the individual components or the two combinations of the three components.
本発明の主なる特徴及び態様は以下の通りである。The main features and aspects of the invention are as follows.
１、水系に
（ｉ）カルボン酸−及びホスフオン酸基である少なくと
も３個の酸基を含み、少なくとも一つの酸基はカルボン
酸基であり、及び少なくとも一つの酸基はホスフオン酸
基であり、少なくとも該３個の酸基は炭素原子に結合し
ている、ホス７オノカルポン酸、又はその水溶性の塩、
（ｉｉ）式：
％式％（）
上式中
Ｒ４及びＲ２は独立に水素、アルキル、特にｌないし４
炭素原子のアルキル、
−（ｃ Ｈり、 Ｐ ０３Ｈｚ、又は−（ＣＨり、ＣＯ
ＯＨを表し、及びｎはｌ又は２である、
を有するアミノホスフォン酸又はその水溶性の塩、及び
（ｉｉｉ）式
％式％）
上式中
Ｒ１、Ｒ１及びｎは上記の通りである、のアミノホスフ
ォン酸酸化物、又はその水溶性の塩、
を添加することから成る、水系を処理する方法。1. The aqueous system contains (i) at least three acid groups that are carboxylic acid and phosphonic acid groups, at least one acid group is a carboxylic acid group, and at least one acid group is a phosphonic acid group; phos-7-onocarboxylic acid, or a water-soluble salt thereof, in which at least the three acid groups are bonded to carbon atoms; , especially l to 4
Alkyl of a carbon atom, -(c H ri, P 03Hz, or -(CH ri, CO
represents OH, and n is l or 2; or a water-soluble salt thereof.
２、アミノホスホン酸がアミノトリス（メチレンホスホ
ン酸）であり、アミノホスホン酸酸化物がアミノトリス
（メチレンホスホン酸）オキシドであり、及びホスホノ
カルボン酸が２−ホスホノブタン−１，２，４−１−リ
カルポン酸である、上記ｌに記載の方法。2. The aminophosphonic acid is aminotris(methylenephosphonic acid), the aminophosphonic acid oxide is aminotris(methylenephosphonic acid) oxide, and the phosphonocarboxylic acid is 2-phosphonobutane-1,2,4-1 - The method according to item 1 above, wherein the method is ricarponic acid.
３、上記ｌに記載の成分（ｉ）、（ｉｉ）及び（ｉｉ）
から成る、水系に添加するのに適当な組成物。3. Components (i), (ii) and (ii) described in 1 above
A composition suitable for addition to an aqueous system, consisting of:
Claims (1)
３個の酸基を含み、少なくとも一つの酸基はカルボン酸
基であり、及び少なくとも一つの酸基はホスフォン酸基
であり、少なくとも該３個の酸基は炭素原子に結合して
いる、ホスフォノカルボン酸、又はその水溶性の塩、 （ｉｉ）式： Ｈ＿２−ＰＯ＿３（ＣＨ＿２）＿ｎ−Ｎ（Ｒ＿１）（Ｒ
＿２）上式中 Ｒ＿１及びＲ＿２は独立に水素、アルキル、特に１ない
し４炭素原子のアルキル、 −（ＣＨ＿２）＿ｎＰＯ＿３Ｈ＿２、又は−（ＣＨ＿２
）＿ｎＣＯＯＨを表し、及びｎは１又は２である、 を有するアミノホスフォン酸又はその水溶性の塩、及び （ｉｉｉ）式 Ｈ＿２−ＰＯ＿３（ＣＨ＿２）＿ｎ−Ｎ（−→Ｏ）（Ｒ
＿１）（Ｒ＿２）上式中 Ｒ＿１、Ｒ＿２及びｎは上記の通りである、のアミノホ
スフォン酸酸化物、又はその水溶性の塩、 を添加することから成る、水系を処理する方法。 ２、特許請求の範囲１項に記載の成分（ｉ）、（ｉｉ）
及び（ｉｉｉ）から成る、水系に添加するのに適当なス
レール防止用組成物。[Claims] 1. The aqueous system contains (i) at least three acid groups that are carboxylic acid and phosphonic acid groups, at least one acid group is a carboxylic acid group, and at least one acid group is a phosphonic acid group; a phosphonocarboxylic acid or a water-soluble salt thereof, which is an acid group, and at least the three acid groups are bonded to carbon atoms, (ii) Formula: H_2-PO_3(CH_2)_n-N(R_1) (R
_2) In the above formula, R_1 and R_2 are independently hydrogen, alkyl, especially alkyl of 1 to 4 carbon atoms, -(CH_2)_nPO_3H_2, or -(CH_2
)_nCOOH, and n is 1 or 2, and (iii) an aminophosphonic acid or a water-soluble salt thereof having the formula H_2-PO_3(CH_2)_n-N(-→O)(R
_1) (R_2) A method for treating an aqueous system, comprising adding an aminophosphonic acid oxide, or a water-soluble salt thereof, wherein R_1, R_2 and n are as described above. 2. Components (i) and (ii) according to claim 1
and (iii), an anti-thrail composition suitable for addition to an aqueous system.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8829612A GB2227997B (en) | 1988-12-20 | 1988-12-20 | Scale control |
| GB8829612.4 | 1988-12-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02227195A true JPH02227195A (en) | 1990-09-10 |
Family
ID=10648747
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1328627A Pending JPH02227195A (en) | 1988-12-20 | 1989-12-20 | Scale prevention method |
Country Status (9)
| Country | Link |
|---|---|
| US (2) | US5049304A (en) |
| EP (1) | EP0375385B1 (en) |
| JP (1) | JPH02227195A (en) |
| AT (1) | ATE97118T1 (en) |
| CA (1) | CA2005949A1 (en) |
| DE (1) | DE68910655T2 (en) |
| ES (1) | ES2059790T3 (en) |
| GB (1) | GB2227997B (en) |
| ZA (1) | ZA899763B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5167866A (en) * | 1989-12-15 | 1992-12-01 | W. R. Grace & Co. Conn. | Control of corrosion in aqueous systems using certain phosphonomethyl amine oxides |
| ZA905799B (en) * | 1989-12-15 | 1991-05-29 | Grace W R & Co | Control of scale in aqueous systems using certain phosphonomethyl amine oxides |
| DE4131912C2 (en) * | 1991-09-25 | 1999-01-07 | Budenheim Rud A Oetker Chemie | Carboxyalkane aminomethanephosphonic acid mixtures |
| US5322636A (en) * | 1992-03-30 | 1994-06-21 | Calgon Corporation | Polyether polyamino methylene phosphonate n-oxides for high pH scale control |
| US5433886A (en) * | 1992-05-07 | 1995-07-18 | Calgon Corporation | Stabilization of polyether polyamino methylene phosphonate scale inhibitors against degradation by bromine and chlorine biocides |
| US5439611A (en) * | 1992-05-07 | 1995-08-08 | Calgon Corporation | Stabilization of hydroxyalkylidene phosphonate scale inhibitors against degradation by bromine and chlorine biocides |
| US5449476A (en) * | 1992-05-07 | 1995-09-12 | Calgon Corporation | Stabilization of aminomethylene phosphonate scale inhibitors against degradation by bromine and chlorine biocides |
| US6083403A (en) * | 1998-11-05 | 2000-07-04 | Nalco Chemical Company | Stabilized substituted aminomethane-1, 1-diphosphonic acid n-oxides and use thereof in preventing scale and corrosion |
| US6207079B1 (en) * | 1999-01-28 | 2001-03-27 | Ashland Inc. | Scale and/or corrosion inhibiting composition |
| US20100197545A1 (en) | 2009-01-30 | 2010-08-05 | Ecolab USA | High alkaline detergent composition with enhanced scale control |
| CA2755841C (en) * | 2009-04-21 | 2021-08-17 | Ecolab Usa Inc. | Methods and apparatus for controlling water hardness |
| US8883035B2 (en) | 2009-07-27 | 2014-11-11 | Ecolab Usa Inc. | Formulation of a ware washing solid controlling hardness |
| US9193610B2 (en) | 2011-08-10 | 2015-11-24 | Ecolab USA, Inc. | Synergistic interaction of weak cation exchange resin and magnesium oxide |
| CN114262072A (en) * | 2019-01-31 | 2022-04-01 | 陈建华 | Self-adaptive hardness-reducing type ash water scale inhibition and dispersion agent for coal gasification black ash water and application |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3429914A (en) * | 1964-09-03 | 1969-02-25 | Monsanto Co | Organo-phosphono-amine oxides |
| CA813301A (en) * | 1966-09-06 | 1969-05-20 | E. Zimmerer Roger | Detergent composition |
| US3483178A (en) * | 1968-04-18 | 1969-12-09 | Monsanto Co | Esters,salts,and acids of organo-phosphono-amine oxides |
| US3671448A (en) * | 1970-09-10 | 1972-06-20 | Monsanto Co | Methods of scale inhibition using substoichiometric amounts of amino alcohol and phosphonic acids |
| US3891568A (en) * | 1972-08-25 | 1975-06-24 | Wright Chem Corp | Method and composition for control of corrosion and scale formation in water systems |
| DE2325829C2 (en) * | 1973-05-22 | 1982-04-01 | Henkel KGaA, 4000 Düsseldorf | Sequestrants |
| DE2360711A1 (en) * | 1973-12-06 | 1975-06-12 | Henkel & Cie Gmbh | Medicaments for controlling calcium depositon or dissolution - contg aminoalkane-phosphonic acids |
| US4008164A (en) * | 1974-03-21 | 1977-02-15 | Nalco Chemical Company | Process for scale inhibition |
| US4406811A (en) * | 1980-01-16 | 1983-09-27 | Nalco Chemical Company | Composition and method for controlling corrosion in aqueous systems |
| US4566974A (en) * | 1983-06-28 | 1986-01-28 | The B. F. Goodrich Company | Method of inhibiting scale with copolymer |
| US4600524A (en) * | 1983-12-08 | 1986-07-15 | W. R. Grace & Co. | Composition and method for inhibiting scale |
| US4640793A (en) * | 1984-02-14 | 1987-02-03 | Calgon Corporation | Synergistic scale and corrosion inhibiting admixtures containing carboxylic acid/sulfonic acid polymers |
| US4563284A (en) * | 1984-08-06 | 1986-01-07 | The B. F. Goodrich Company | Inhibition of salt precipitation in aqueous systems |
| DE3526640A1 (en) * | 1985-07-25 | 1987-01-29 | Benckiser Knapsack Gmbh | CORROSION AND STONE PROTECTION AGENTS FOR DOMESTIC WATER SYSTEMS |
| US4806259A (en) * | 1987-06-15 | 1989-02-21 | The B. F. Goodrich Company | Membrane cleaning compositions containing phosphorous compounds |
-
1988
- 1988-12-20 GB GB8829612A patent/GB2227997B/en not_active Expired - Lifetime
-
1989
- 1989-12-19 CA CA002005949A patent/CA2005949A1/en not_active Abandoned
- 1989-12-20 DE DE89313326T patent/DE68910655T2/en not_active Expired - Fee Related
- 1989-12-20 US US07/454,101 patent/US5049304A/en not_active Expired - Fee Related
- 1989-12-20 ES ES89313326T patent/ES2059790T3/en not_active Expired - Lifetime
- 1989-12-20 EP EP89313326A patent/EP0375385B1/en not_active Expired - Lifetime
- 1989-12-20 JP JP1328627A patent/JPH02227195A/en active Pending
- 1989-12-20 AT AT89313326T patent/ATE97118T1/en not_active IP Right Cessation
- 1989-12-20 ZA ZA899763A patent/ZA899763B/en unknown
-
1991
- 1991-05-24 US US07/705,445 patent/US5093005A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| ZA899763B (en) | 1990-09-26 |
| US5049304A (en) | 1991-09-17 |
| ATE97118T1 (en) | 1993-11-15 |
| US5093005A (en) | 1992-03-03 |
| EP0375385B1 (en) | 1993-11-10 |
| GB2227997A (en) | 1990-08-15 |
| GB2227997B (en) | 1992-04-15 |
| GB8829612D0 (en) | 1989-02-15 |
| EP0375385A2 (en) | 1990-06-27 |
| DE68910655T2 (en) | 1994-02-24 |
| ES2059790T3 (en) | 1994-11-16 |
| CA2005949A1 (en) | 1990-06-20 |
| DE68910655D1 (en) | 1993-12-16 |
| EP0375385A3 (en) | 1990-09-19 |
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